CN105153466A - Intumescent flame retardant modified montmorillonite and preparation method thereof - Google Patents

Intumescent flame retardant modified montmorillonite and preparation method thereof Download PDF

Info

Publication number
CN105153466A
CN105153466A CN201510654183.3A CN201510654183A CN105153466A CN 105153466 A CN105153466 A CN 105153466A CN 201510654183 A CN201510654183 A CN 201510654183A CN 105153466 A CN105153466 A CN 105153466A
Authority
CN
China
Prior art keywords
flame retardant
expansion type
type flame
modified montmorillonite
retardant modified
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510654183.3A
Other languages
Chinese (zh)
Other versions
CN105153466B (en
Inventor
俞金娜
黄国波
汪鹏飞
陈倩滢
谷新剑
罗仁新
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taizhou University
Original Assignee
Taizhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taizhou University filed Critical Taizhou University
Priority to CN201510654183.3A priority Critical patent/CN105153466B/en
Publication of CN105153466A publication Critical patent/CN105153466A/en
Application granted granted Critical
Publication of CN105153466B publication Critical patent/CN105153466B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention relates to a flame retardant, in particular to intumescent flame retardant modified montmorillonite and a preparation method thereof. The structure of the intumescent flame retardant modified montmorillonite is shown in the formula (I) (in the description), wherein in the formula (I), the strip-shaped object refers to the montmorillonite, and the compound grafted onto the surface of the montmorillonite is an intumescent flame retardant. In the intumescent flame retardant modified montmorillonite, the intumescent flame retardant is connected with the montmorillonite through chemical bonds. The intumescent flame retardant modified montmorillonite is suitable for high polymer material modification with the processing temperature within 320 DEG C, and is insoluble in water and organic solvents.

Description

A kind of expansion type flame retardant modified montmorillonite and preparation method thereof
Technical field
The present invention relates to a kind of fire retardant, be specifically related to a kind of expansion type flame retardant modified montmorillonite and preparation method thereof.
Background technology
During the burning of polymer-montmorillonoid matrix material, polymer surfaces forms the silicate layer of charcoal of porous, and this layer can improve the flame retardant properties of material as excellent insulation and mass transfer barrier, the effusion of the volatile products produced when delaying material thermal decomposition.Utilize polynite and the composite common modified polyurethane of expansion type flame retardant (as ammonium polyphosphate, polyphosphoric acid melamine etc.), nylon 6, unsaturated polyester, epoxy resin etc.In nano composite polymer-montmorillonoid material, add conventional flame retardants is not reducing in other situation of flame retardant grade, and the consumption (with pure Polymers Phase ratio) of fire retardant obviously reduces, and visible fire retardant and polynite have certain cooperative flame retardant effect.But this system is just obtained by the simple physical blending of three, polynite and expansion type flame retardant are difficult to realize dispersed in polymeric matrix, have a strong impact on the performance of both cooperative flame retardant effects in material combustion process.Utilize the feature of polynite surface containing hydroxyl, expansion type flame retardant carries out organic modification by condensation reaction to polynite surface, the expansion type flame retardant modified montmorillonite of gained by suitable technique (fusion intercalation or monomer polymerization intercalation etc.), dispersed in polymeric matrix of the expansion type flame retardant achieving polynite and its surface of enrichment.
Single component expansion type flame retardant collects acid source, charcoal source, source of the gas in same intramolecular fire retardant.Compared with polycomponent expansion type flame retardant, there is better thermostability and resistance to water soak, better matrix phase capacitive and resistance to surface transport property; When flame-retardant polymer, three elements can more closely react, and flame retarding efficiency is higher.So single component expansion type flame retardant is one of main development direction of halogen-free expanded flame-retardant agent.
Summary of the invention
The invention provides a kind of dispersed and consistency is better, the better expansion type flame retardant modified montmorillonite of fire retardation.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of expansion type flame retardant modified montmorillonite, described expansion type flame retardant modified montmorillonite, its structure is such as formula shown in (I):
in formula (I), bar represents polynite, and the compound being grafted on polynite surface is expansion type flame retardant.Described expansion type flame retardant modified montmorillonite, its expansion type flame retardant is connected with polynite by chemical bond.It is polymer modification within 320 DEG C that described expansion type flame retardant modified montmorillonite is applicable to processing temperature.Described expansion type flame retardant modified montmorillonite is water insoluble, organic solvent.
Through the polynite of expansion type flame retardant surface organic process, not only fall and improve its dispersiveness in polymeric matrix and consistency, and the expansion type flame retardant of load on polynite surface can promote the formation of layer of charcoal, improving the fire retardation to polymeric matrix, providing a kind of new approach for solving above-mentioned montmorillonite flame-retardant modified polymer material Problems existing.
As preferably, in expansion type flame retardant modified montmorillonite, the mass content of expansion type flame retardant is 3 ~ 40%, is preferably 20 ~ 30%.
As preferably, expansion type flame retardant is reacted by the silane coupling agent of P contained compound and amino-contained to form, and P contained compound is 2-oxo-2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane, the silane coupling agent of amino-contained is N-aminoethyl-γ-aminopropyltrimethoxysilane.
A kind of preparation method of described expansion type flame retardant modified montmorillonite, the method is specifically: the silane coupling agent of amino-contained and polynite are reacted, obtained silane coupler modified polynite, then with 2-oxo-2-chloro-5,5-dimethyl-1, the obtained expansion type flame retardant modified montmorillonite of 3,2-dioxaphosphorinane (DPPC) reaction.
As preferably, the method is specifically: polynite joined in toluene, be moved into after ultrasonic disperse and be equipped with in the dry four-hole bottle of mechanical stirring, thermometer, reflux condensing tube and dropping funnel, the mixed solution of N-aminoethyl-γ-aminopropyltrimethoxysilane and toluene is dripped under room temperature, and rise to reflux temperature, continue stirring reaction to abundant, then 30 DEG C-50 DEG C are cooled to, drip 2-oxo-2-chloro-5,5-dimethyl-1, the mixed solution of 3,2-dioxaphosphorinane (DPPC), triethylamine and toluene, continues reaction to abundant; Then the slurries be obtained by reacting are filtered, organic solvent washing, dry, obtain expansion type flame retardant modified montmorillonite.
As preferably, the mass ratio of polynite, N-aminoethyl-γ-aminopropyltrimethoxysilane, chloro-5,5-dimethyl-1,3, the 2-dioxaphosphorinanes (DPPC) of 2-oxo-2-and triethylamine is 8 ~ 65:0.753:1.247:3.6 ~ 5.
Expansion type flame retardant modified montmorillonite described in use makes an application for urethane/expansion type flame retardant modified montmorillonite matrix material, adds the expansion type flame retardant modified montmorillonite of significant quantity in the preparation of urethane.
Compared with prior art, beneficial effect of the present invention is embodied in following several respects: the expansion type flame retardant modified montmorillonite that the present invention obtains, utilize expansion type flame retardant to carry out chemically modified to polynite, improve the lipophilicity on polynite surface, be conducive to polynite and disperse in the polymer; Expansion type flame retardant modified montmorillonite of the present invention adopts halogen-free flame-retardant system, decreases " the secondary harm " in materials'use process; Fire retardant of the present invention utilizes expansion type flame retardant and the effect of polynite cooperative flame retardant, improves the flame retardant effect to macromolecular material, reduces the usage quantity of fire retardant at macromolecular material, reduces the cost of fire retardant material.The polynite containing Long carbon chain modifier modification compared by fire retardant of the present invention, and expansion type flame retardant increases the polarity of organ-mmt part, thus improves the high molecular consistency with polarity, widens its range of application.Fire retardant of the present invention is not halogen-containing, good flame retardation effect, applied widely, meet environmental requirement.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of expansion type flame retardant modified montmorillonite of the present invention.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail.Should be appreciated that enforcement of the present invention is not limited to the following examples, any pro forma accommodation make the present invention and/or change all will fall into scope.
In the present invention, if not refer in particular to, all parts, per-cent are weight unit, and the equipment adopted and raw material etc. all can be buied from market or this area is conventional.Method in following embodiment, if no special instructions, is the ordinary method of this area.
Embodiment 1
8g polynite is joined in 150mL toluene, ultrasonic disperse is after 30 minutes, be moved into and be equipped with in the dry four-hole bottle of mechanical stirring, thermometer, reflux condensing tube and dropping funnel, 0.753gN-aminoethyl-γ-aminopropyltrimethoxysilane and 15mL toluene mixture liquid is dripped under room temperature, and rise to reflux temperature, continue stirring reaction 6 hours, then 45 DEG C are cooled to, drip 1.247g2-oxo-2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane, 3.6g triethylamine and 15mL toluene mixture liquid, continue reaction 6 hours.Then the suspension filtered be obtained by reacting, methyl alcohol repetitive scrubbing is used, and in the baking oven of 80 DEG C dry 24 hours, obtained expansion type flame retardant modified montmorillonite, wherein the mass content of expansion type flame retardant is 20%.
Embodiment 2
6.467g polynite is joined in 100mL toluene, ultrasonic disperse is after 30 minutes, be moved into and be equipped with in the dry four-hole bottle of mechanical stirring, thermometer, reflux condensing tube and dropping funnel, 0.0753gN-aminoethyl-γ-aminopropyltrimethoxysilane and 10mL toluene mixture liquid is dripped under room temperature, and rise to reflux temperature, continue stirring reaction 6 hours, be cooled to 50 DEG C, drip 0.1247g2-oxo-2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane, 0.5g triethylamine and 10mL toluene mixture liquid, continue reaction 4 hours.Then the suspension filtered be obtained by reacting, methyl alcohol repetitive scrubbing is used, and in the baking oven of 80 DEG C dry 24 hours, obtained expansion type flame retardant modified montmorillonite, wherein the mass content of expansion type flame retardant is 3%.
Embodiment 3
6g polynite is joined in 80mL toluene, ultrasonic disperse is after 30 minutes, be moved into and be equipped with in the dry four-hole bottle of mechanical stirring, thermometer, reflux condensing tube and dropping funnel, 2.188gN-aminoethyl-γ-aminopropyltrimethoxysilane and 20mL toluene mixture liquid is dripped under room temperature, and rise to reflux temperature, continue stirring reaction 6 hours, be cooled to 30 DEG C, drip 2.812g2-oxo-2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane, 5.4g triethylamine and 30mL toluene mixture liquid, continue reaction 5 hours.Then the suspension filtered be obtained by reacting, methyl alcohol repetitive scrubbing is used, and in the baking oven of 80 DEG C dry 24 hours, obtained expansion type flame retardant modified montmorillonite, wherein the mass content of expansion type flame retardant is 40%.
Embodiment 4
9g polynite is joined in 145mL toluene, ultrasonic disperse is after 30 minutes, be moved into and be equipped with in the dry four-hole bottle of mechanical stirring, thermometer, reflux condensing tube and dropping funnel, 0.3765gN-aminoethyl-γ-aminopropyltrimethoxysilane and 8mL toluene mixture liquid is dripped under room temperature, and rise to reflux temperature, continue stirring reaction 6 hours, be cooled to 30 DEG C, drip 0.6235g2-oxo-2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane, 2.2g triethylamine and 30mL toluene mixture liquid, continue reaction 7 hours.Then the suspension filtered be obtained by reacting, methyl alcohol repetitive scrubbing is used, and in the baking oven of 80 DEG C dry 24 hours, obtained expansion type flame retardant modified montmorillonite, wherein the mass content of expansion type flame retardant is 10%.
Embodiment 5: the application of expansion type flame retardant modified montmorillonite
The synthetic operation of expansion type flame retardant modified montmorillonite is the infrared spectrogram of expansion type flame retardant modified montmorillonite with embodiment 1, Fig. 1.100g polyester polyol (molecular weight is 2000) is at 110 DEG C, dewater 10 hours under vacuum tightness 0.08MPa condition, then 70 DEG C are cooled to, add 1.35g1, 4-butyleneglycol and 12.47g expansion type flame retardant modified montmorillonite mix, add 10.9g hexamethylene diisocyanate again, 80 DEG C of reaction deaerations 0.5 hour (vacuum tightness is 0.095MPa) after 1.5 hours, be cast in the mould of preheating, at 120 DEG C of reaction 30min, 8 ~ 16 hours are left standstill in 80 DEG C after the demoulding, urethane/expansion type flame retardant modified montmorillonite matrix material can be obtained, the result that cone calorimetry measures the fire-retardant performance of this matrix material is as shown in table 1.
Table 1
Note: polyurethane/organic montmorillonite fire-retardant composite material: the mass ratio of organo montmorillonite and urethane is 8:2, organo montmorillonite is the polynite of cetyl trimethylammonium bromide organic-treating, and wherein the mass content of cetyl trimethylammonium bromide is 20%; The mass ratio of expansion type flame retardant modified montmorillonite and urethane is 10:1, and in expansion type flame retardant modified montmorillonite, the mass content of expansion type flame retardant is 20%.
Known by table 1, compared with urethane, the heat release rate peak value that with the addition of the urethane/expansion type flame retardant modified montmorillonite matrix material of expansion type flame retardant modified montmorillonite reduces 40.0%, burning time extends about 12 seconds, Thermal release total amount, specific extinction area average, mass loss mean rate all have and decline in various degree, show that expansion type flame retardant modified montmorillonite has significant fire retardation to urethane, and be better than same based flame retardant organo montmorillonite.
Above-described embodiment is one of the present invention preferably scheme, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.

Claims (7)

1. an expansion type flame retardant modified montmorillonite, is characterized in that: described expansion type flame retardant modified montmorillonite, and its structure is such as formula shown in (I):
in formula (I), bar represents polynite, and the compound being grafted on polynite surface is expansion type flame retardant.
2. expansion type flame retardant modified montmorillonite according to claim 1, is characterized in that: in expansion type flame retardant modified montmorillonite, and the mass content of expansion type flame retardant is 3 ~ 40%.
3. expansion type flame retardant modified montmorillonite according to claim 1, it is characterized in that: expansion type flame retardant is formed by the silane coupling agent reaction of P contained compound and amino-contained, P contained compound is 2-oxo-2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane, the silane coupling agent of amino-contained is N-aminoethyl-γ-aminopropyltrimethoxysilane.
4. the preparation method of an expansion type flame retardant modified montmorillonite according to claim 1, it is characterized in that the method specifically: the silane coupling agent of amino-contained and polynite are reacted, obtained silane coupler modified polynite, then with 2-oxo-2-chloro-5,5-dimethyl-1, the obtained expansion type flame retardant modified montmorillonite of 3,2-dioxaphosphorinane (DPPC) reaction.
5. the preparation method of expansion type flame retardant modified montmorillonite according to claim 4, it is characterized in that: polynite is joined in toluene, be moved into after ultrasonic disperse and mechanical stirring is housed, thermometer, in the dry four-hole bottle of reflux condensing tube and dropping funnel, the mixed solution of N-aminoethyl-γ-aminopropyltrimethoxysilane and toluene is dripped under room temperature, and rise to reflux temperature, continue stirring reaction to abundant, then 30 DEG C-50 DEG C are cooled to, drip 2-oxo-2-chloro-5, 5-dimethyl-1, 3, 2-dioxaphosphorinane (DPPC), the mixed solution of triethylamine and toluene, continue reaction to abundant, then the slurries be obtained by reacting are filtered, organic solvent washing, dry, obtain expansion type flame retardant modified montmorillonite.
6. the preparation method of expansion type flame retardant modified montmorillonite according to claim 5, it is characterized in that: polynite, N-aminoethyl-γ-aminopropyltrimethoxysilane, 2-oxo-2-chloro-5,5-dimethyl-1, the mass ratio of 3,2-dioxaphosphorinane (DPPC) and triethylamine is 8 ~ 65:0.753:1.247:3.6 ~ 5.
7. make an application for urethane/expansion type flame retardant modified montmorillonite matrix material of expansion type flame retardant modified montmorillonite according to claim 1, it is characterized in that: the expansion type flame retardant modified montmorillonite adding significant quantity in the preparation of urethane.
CN201510654183.3A 2015-10-11 2015-10-11 A kind of expansion type flame retardant modified montmorillonite and preparation method thereof Active CN105153466B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510654183.3A CN105153466B (en) 2015-10-11 2015-10-11 A kind of expansion type flame retardant modified montmorillonite and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510654183.3A CN105153466B (en) 2015-10-11 2015-10-11 A kind of expansion type flame retardant modified montmorillonite and preparation method thereof

Publications (2)

Publication Number Publication Date
CN105153466A true CN105153466A (en) 2015-12-16
CN105153466B CN105153466B (en) 2018-09-18

Family

ID=54794537

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510654183.3A Active CN105153466B (en) 2015-10-11 2015-10-11 A kind of expansion type flame retardant modified montmorillonite and preparation method thereof

Country Status (1)

Country Link
CN (1) CN105153466B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109054867A (en) * 2018-08-21 2018-12-21 徐培培 A kind of environmentally friendly fire resistant flame retardant packet for cable shaft
CN109629024A (en) * 2018-12-10 2019-04-16 天津工业大学 Dendritic phosphorous-nitrogen system bittern-free fire retardant and its preparation method and application

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101624403A (en) * 2009-08-10 2010-01-13 浙江工业大学 Phosphorus-nitrogen quaternary ammonium as well as preparation method and application thereof
CN102358784A (en) * 2011-08-25 2012-02-22 贵州省复合改性聚合物材料工程技术研究中心 Preparation method for nano-montmorillonite modified organophosphate nucleating agent
CN102757581A (en) * 2012-07-31 2012-10-31 华南理工大学 Intumescent flame retardant functional silicate and preparation method thereof
CN103224531A (en) * 2013-02-21 2013-07-31 吉林市吉溧化工有限责任公司 Synthetic method for P- and N-containing fire retardant

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101624403A (en) * 2009-08-10 2010-01-13 浙江工业大学 Phosphorus-nitrogen quaternary ammonium as well as preparation method and application thereof
CN102358784A (en) * 2011-08-25 2012-02-22 贵州省复合改性聚合物材料工程技术研究中心 Preparation method for nano-montmorillonite modified organophosphate nucleating agent
CN102757581A (en) * 2012-07-31 2012-10-31 华南理工大学 Intumescent flame retardant functional silicate and preparation method thereof
CN103224531A (en) * 2013-02-21 2013-07-31 吉林市吉溧化工有限责任公司 Synthetic method for P- and N-containing fire retardant

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109054867A (en) * 2018-08-21 2018-12-21 徐培培 A kind of environmentally friendly fire resistant flame retardant packet for cable shaft
CN109054867B (en) * 2018-08-21 2020-12-15 阜阳创启工艺品有限公司 Environment-friendly fire-resistant flame-retardant bag for cable well
CN109629024A (en) * 2018-12-10 2019-04-16 天津工业大学 Dendritic phosphorous-nitrogen system bittern-free fire retardant and its preparation method and application

Also Published As

Publication number Publication date
CN105153466B (en) 2018-09-18

Similar Documents

Publication Publication Date Title
CN102010585B (en) Preparation method of efficient and environment-friendly composite fire retardant
CN102585347B (en) Halogen-free intumescent flame-retardant polypropylene mixture and preparation method thereof
CN102838778A (en) Preparation method of nitrogen and phosphorus fire retardant, nitrogen and phosphorus fire retardant and application thereof
CN102516603A (en) Preparation method of microencapsulated gradient halogen-free flame retardant system
CN104262620B (en) A kind of expanded polystyrene veneer melt-drip resistant inflaming retarding agent and its preparation method
CN108299633B (en) ferrocene-DOPO double-base polyester type flame-retardant smoke suppressant and preparation method thereof and application of ferrocene-DOPO double-base polyester type flame-retardant smoke suppressant in flame-retardant polymer
CN104262398A (en) Phosphorus-nitrogen type flame retardant containing active double bond as well as preparation method and application thereof
CN105254923A (en) Preparation method of phosphorus-nitrogen compound grafted hydrotalcite flame retardant
CN102863905A (en) Polyhedral oligomeric silsesquioxane (POSS) contained environment-friendly inflaming retarding wood adhesive and preparation method thereof
CN103756015A (en) Hyperbranched triazine charring agent microcapsule flame retardant and preparation method thereof
CN105566682A (en) Nucleotide-based flame retardant microsphere and preparation method and application thereof
CN105153466A (en) Intumescent flame retardant modified montmorillonite and preparation method thereof
CN101982497A (en) Flame-retardant acrylonitrile-butadiene-styrene (ABS) composite material
CN105153467B (en) A kind of expansion type flame retardant functionalization hydrotalcite fire retardant and preparation method thereof
Liu et al. Synergistic effect of nano magnesium amino-tris-(methylenephosphonate) and expandable graphite on improving flame retardant, mechanical and thermal insulating properties of rigid polyurethane foam
CN105175786A (en) Montmorillonite composite flame retardant and preparation method thereof
CN105153468B (en) A kind of compound loaded montmorillonite flame-retardant agent of phosphorus nitrogen silicon systems and preparation method thereof
CN101891896B (en) Expansible fire retardant containing fluorine-phosphorus-nitrogen oligomer and preparation method thereof
CN106380595A (en) Preparation method of hyperbranched flame retardant and application of hyperbranched flame retardant in polyurethane
CN105199146A (en) Hydrotalcite composite flame retardant and preparation method thereof
CN105924645A (en) Halogen-free expanding flame retardant containing polymeric macromolecule triazine rings and preparation method of halogen-free expanding flame retardant
CN105367604A (en) Phosphorus-nitrogen-containing star-type charring agent and preparation method thereof
CN105153465A (en) Phosphorus-nitrogen-silicon compound modified hydrotalcite flame retardant and preparation method thereof
CN107652324B (en) Three-source-in-one expansion type fire retardant and its synthetic method and application
CN105175785A (en) Phosphorus-nitrogen compound intercalated hydrotalcite and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
C06 Publication
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
GR01 Patent grant
GR01 Patent grant